Dyestuffs of the stilbene series and process of making same



Patented May 31, 1932 UNITED 7 STATES PATENT OFFICE MAX SCI-IMID, OF RIEHEN, NEAR BASEL, SWITZERLAND, ASSIGNOR TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND DYEST'UFFS OF THE STILBENE SERIES AND PROCESS OF MAKING SAME No Drawing. Original application filed March 12, 1930, Serial No. 435,354, and in Switzerland March 16,

1929. Divided and this application filed March 26, 1931.

This application is divisional of application Serial No. 435,354, filed March 12, 1930.

The present invention relates to the manufacture of new dyestuffs. It comprises the process of making these dyestuffs, the dyestuffs themselves, and the material dyed with the new dyestuffs.

In U. S. Patent No. 903,284 cotton dyestulfs are described which are produced by condensing in an alkaline medium one molecule of a monoamino-azo-dyestuif with one molecule of p-p-dinitrostilbene-o-o-disulfonic acid, p-p'-dinitrodibenzyl-o-o-disulfonic acid or a conversion product of the pnitrotoluene-sulfonic acid.

The present invention is based on the discovery that new dyestuffs of great technical importance are obtained by treating the new technically valuable products, which are made according to the process of application Serial No. 435,354 of March 12, 1930,'by condensing in a closed system at 115 to 150 C., and in various stoichiometrical proportions, aromatic amino-compounds of the benzene and naphthalene series with dinitrostilbenedisulfonic acid, dinitrodibenzylsulfonic acid or a conversion, product of para-nitrotoluenesulfonic acid of the general formula wherein at least one benzene nucleus contains a sulfo-group, and w stands for a bridge consisting of two carbon atoms each of which is linked with one of the benzene nuclei, with oxidizing agents.

The expression oxidizing agents used above applies to such substances which are usually used for oxidizing stilbene dyestuffs, i. e. hypochlorites or alkaline solutions of the halogens.

The products obtained by the invention differ from the corresponding products made by oxidation of the condensation products, which themselves have been produced in an open vessel, in that the tints which they produce are deeper in tone and of enhanced fastness to light. These improvements, which 2 could not be foreseen, constitute an important Serial No. 525,539.

technical advance in the manufacture of the so-called stilbene dyestuffs.

The following examples illustrate the invention, the parts being by weight 2- E'wample 1 An autoclave provided with a stirrer is charged with 723 parts of the saponified dyestuff from diazotized metanilic acid and the sodium salt of ortho-anisidine-w-methanesulfonic acid, 430 parts of sodium dinitrostilbenedisulfonate, 10000 parts of water and 1000 parts of caustic soda solution of36 B. The temperature is raised to 120-125 C. and the condensation which takes place is continued for 6 hours at this temperature. After cooling, the caustic soda solution is neutralized by acid, the partially separated dyestuff is wholly separated by salting out in the usual manner and filtered. The filtered dyestufi is stirred up in 6000 parts of water and heated to 0., whereuponthe whole is treated for 1 hour at this temperature with 2400 parts of a sodium hypochlorite solution containing 13.5 per cent. of active chlorine. The partially separated dyestufli' is salted out as usual. The dried dyestulf is a red-brown powder soluble in water and dilute alkalies to a red-orange solution and in concentrated sulfuric acid to a green solution. It dyes cotton pure orangered tints fast to light and alkali.

Products yielding orange-red to bluish shades of good fastness to light and alkali are obtained by treating the corresponding condensation products from amino-azo-dyestuffs which derive from 1-methyl-3-amino- 4-alkoxy-benzene, 1 4dimethoXy-2-aminobenzene, or from a-naphthylamine with hypohalites.

The operation is similar with other azodyestuffs containingamino-groups, such as those which are made from diazo-components, such as .aniline4-sulfonic acid, orthotoluidine-4-sulfonic acid, 2-chloro-1-aminohenzene-5-sulfonic acid, 4-chloro-1-aminobenzene-8-sulfonic acid, l-amino-naphthalene-5-sulfonic acid, 1-aminonaphthalene-6- sulfonic acid,2-aminonaphthalene3 6-disulfonic acid, and from coupling components,

ll HO;S@N N of German Patent No. 214,658, or if in place of sodium dinitrostilbenedisulfonic acid the salt of dinitrodibenzyldisulfonic acid of the formula OzN CH2-CH N02 is used for the condensation.

Products are obtained which dye cotton yell0w-orange to orange and brown-red tlnts.

E azample 2 An autoclave provided with a stirrer is charged with 672 parts of dehydrothiotoluidinemonosulfonic acid of the probable formula 130 parts of sodium dinitrostilbenedisulfonate, 10000 parts of water, and 1000 parts of caustic soda solution of 36 Be. The temperature is raised to 125-130 0. and the condensation which takes place is continued for 6 hours at this temperature.

The wet and filtered dyestuf'f of the preceding paragraph is stirred up in 20000 parts of water and the temperature raised to -95 0., whereupon 3000 parts of sodium hy 3ochlorite solution containing 13.5 per cent. of

active chlorine are slowly dropped in within 1/ hour, oxidizing being continued for 2 hours at the above temperature. After cooling, the partially separated dyestuff is wholly salted out as usual. The dried dyestuff is a red-orange powder soluble in wate and dilute alkalies to a yellow-orange solution and in concentrated sulfuric acid to a red-violet solution. It dyes cotton orange yellow tints fast to light and alkali.

What I claim is '1. Process for the manufacture of dyestuffs of the stilbene series, consisting in treating with hypohalites the products which are obtained by condensing the conversion products of para-nitrotoluene-sulfonic acid of the general formula wherein each benzene nucleus contains at least one sulfo group, and 0e stands for a bridge consisting of two carbon atoms each of which is linked with one of the benzene nuclei, in an alkaline medium, in a closed system, at to 0., and in various stoichiometrical proportions, with aromatic amino-compounds of the benzene and naphthalene series.

'2. Process for the manufacture of dyestuffs of the stilbene series, consisting in treating with hypohalites the products which are obtained by condensing the conversion products of para-nitrotoluene-sulfonic acid of the general formula wherein each benzene nucleus contains at least one sulfo group, and 0a stands for a bridge consisting of two carbon atoms each of which is linked with one of the benzene nuclei, in an alkaline medium, in a closed system, at 115 to 150 0., and in various stoichiometrical proportions, with aromatic aminocompounds of the benzene and naphthalene series containing chromophoric groups.

3. Process for the manufacture of dyestuffs of the stilbene series, consisting in treating with hypohalites the products which are obtained by condensingv dinitrostilbenedisulfonic acid of the formula SIO3H S'O H in an alkaline medium, in a closed system, at 115 to 150 0., and in various stoichiometrical proportions, with aromatic amino-compounds of the benzene and naphthalene series containing chromophoric groups.

4. Process for the manufacture of dyestuffs of the stilbene series, consisting in treating with hypochloites the products which are obtained by condensing dinitrostilbenedisulfonic acid of the formula I 30311 sonar in an alkaline medium, in a closed system, at 115 to 150 0., and in various stoichiometrical proportions, with any amino-azo-dyestuif of the benzene and naphthalene series.

5. Process for the manufacture of dyestuffs of the stilbene series, consisting in treating with hypochlorites the products which are obtained by condensing dinitrostilbenedisulfonic acid of the formula in an alkaline medium, in a closed system, at 115 to 150 C., and in various stoichiometrical proportions, with amino-azo-dyestufis of the general formula wherein R and R stand for aromatic nuclei of the benzene and naphthalene series.

6. Process for the manufacture of dyestuffs of the stilbene series, consisting in treating with hypochlorites the products which are obtained by condensing dinitrostilbenedisulfonic acidof the formula OzN scan $0311 V in an alkaline medium, in a closed system, at 115 to 150 (3., and in variousstoichiometrical proportions, with amino-azo-dyestufi's of the general formula wherein R and R stand for aromatic nuclei of the benzene and naphthalene series of which at the most one is a nucleus of the naphthalene series.

7. Process for the manufacture of dyestuffs of the stilbene series, consisting in treating with hypochlorites the products which are obtained by condensing dinitro stilbenedisulfonic acid of the formula OzN QGACHOM).

. in an alkaline medium, in a closed system, at

115 to 150 (1, and in various stoichiometrical proportions, with amino-azo-dyestufi's of the general formula wherein R and R stand for nuclei of the benzene series.

8. As new products the dyestuifs which are formed by condensmg theflconverslon products of para-nitrotoluene-sulfonic acid of the general formula wherein each benzene nucleus contains at least one sulfo group, and a0 stands for a bridge consisting of two carbon atoms each of which is linked with one of the benzene nuclei, in an alkaline medium, in a closed system, at 115 to 150 (1, and in various 7 stoichiometrical proportions, with aromatic amino-compounds of the benzene or naphthalene series, and treating the products thus obtained with hypohalites, which products form dark powders, dissolving in water and T dilute alkalies to brown, red-brown, redorange and yellow-orange solutions, and in concentrated sulfuric acid to blue, green, redviolet, green-blue and Violet solutions, and

dyeing cotton yellow, red-orange, orange,

yellow-orange, orange-brown and red-brown tints.

9. As new products the dyestuffs which are formed by condensing the conversion products of the general formula wherein each benzene nucleus contains at least one sulfo group, and w stands for a bridge consisting of two carbon atoms each of which is linked with one of the benzene nuclei, in an alkaline medium, in a closed system, at 115 to 150 0., and in various stoichiometrical proportions, with aromatic amino-compounds of the benzene and naphthalene series containing chromophoric groups, and treating the products thus obtained with hypohalites, which products form dark powders, dissolving in water and dilute alkalies to red-brown, red-orange and yellow-orange solutions, and in concentrated sulfuric acid to blue, green and green-blue solutions, and dyeing cotton red-orange. orange, yellow-orange, orange-brown and red-brown. tints.

10. As new products the dyestuffs which are formed by condensing dinitrostilbenedisulfonic acid of the formula yellow-orange, orange-brown and red-brown tints.

11. As new products the dyestuffs which concentrated sulfuric acid to blue, green and are formed by condensing dinitrostilbenedisulfonic acid of the formula l 803E 803E I soan soul in an alkaline medium, in a closed system. at 115 to 150 C., and in various stoichiometrical proportions, with an amino-azo-dyestuff of the general formula wherein R and R stand for aromatic nu clei, of the benzene and naphthalene series. and treating the products thus obtained with hypochlorites, which products form dark powders, dissolving in water and dilute alkalies to red-brown, red-orange and yelloworange solutions, and in concentrated sul furic acid to blue, green and green-blue solutions, and dyeing cotton red-orange, orange, yellow-orange, orange-brown and red-brown tints. I

13. As new products the dyestuffs which are formed by condensing dinitrostilbenedisulfonic acid of the formula SO3H 0311 in an alkaline medium in a closed system, at 115 to 150 (1., and in various stoichiometrical proportions, with an ammo-azo-dyestuif of the general formula wherein R5 and R stand for aromatic nuclei of the benzene and naphthalene series of which at the most one is a nucleus of the naphthalene series, and treating the products thus obtained with hypochlorites, which products form dark powders, dissolving in water and dilute alkalies to red-brown. redorange and yellow-orange solutions, and in green-blue solutions, and dyeing cotton redorange, orange, yellow-orange, orangebrown and red-brown tints.

14. As new products the dyestuffs which are formed by condensing dinitrostilbenedisulfonic acid of the formula i SOaH 803E in an alkaline medium, in a closed system, at 115 to 150 0., and in various stoichiometrical proportions, with an amino-azo-dyestuff of the general formula wherein R and R stand for nuclei of the benzene series, and treating the products thus obtained with hypochlorites, which products form dark powders, dissolving in water and dilute alkalies to red-brown, redorange and yellow-orange solutions, and in concentrated sulfuric acid to blue, green and green-blue solutions, and dyeing cotton redorange, orange, yellow-orange, orangebrown and red-brown tints.

15. As new products the dyestuffs which are formed by condensing dinitrostilbenedisulfonic acid of the formula OzN OH=CH NOz in an alkaline medium, in a closed system, at 115 to 150 (1., and in various stoichiometrical portions, with the azo-dyestuff of the formula SO3H OCH;

and treating the products thus obtained with hypochlorites, which products form dark powders, dissolving in water and dilute alkalies to red-orange solutions, and in concen trated sulfuric acid to green solutions, and dyeing cotton red-orange tints very fast to light.

16. As a new product the dyestuff which is formed by condensing dinitrostilbenedisulfonic acid of the formula in an alkaline medium, under pressure, and at 120;to 130 (3., with two molecular proportions of the azo-dyestufls of the formula 503K and treating the productv thus obtained with hypochlorites, which product forms a brown powder, dissolving in water and dilute alkalies to red-orange solutions, and in concentrated sulfuric acid to green solutions, and dyeing cotton red-orange tints very fast to light.

17 As a new product the dyestufi' which is formed by condensing dinitrostilbenedisulfonic acid of the formula SOaH SOzH in an alkaline medium, under pressure, and at to C., with two molecular proportions of the azo-dyestuff of the formula and treating the product thus obtained with hypochlorites, which product forms a brown powder, dissolving in water and dilute alkalies to orange-red solutions, and in concentrated sulfuric acid to greenish-blue solutions, and dyeing cotton orange-red tints very fast to light.

18. As a new product the dyestufi which is formed by condensing dinitrostilbenedisulfonic acid of the formula OMHQNO, SOIH 0:11

in an alkaline medium, under pressure, and at 120 to 130 0., with two molecular proportions of the azo-dyestufi' of the formula and treating the product thus obtained with hypochlorites, which product forms a brown powder, dissolving in water and dilute alka- I lies to red solutions, and in concentrated sulfuric acid to reddish-blue solutions, and dyeing cotton red tints fast to light.

In witness whereof I have hereunto signed my name this 13th day of March, 1931.

MAX SCHMID. 

